KR20200037260A - Aqueous coating composition - Google Patents

Abstract

(I)
여기서, R₁은 페닐기 또는 페닐 치환된 알킬기이고; m1은 1, 2, 3 또는 4이고; R₂는 알킬 또는 치환된 알킬이고; m2는 0 또는 1이고; R₃은 수소 또는 C₁-C₂₀ 알킬기이고; R₄는 수소 또는 C₁-C₂₀ 알킬기이고; A는 2 내지 4개의 탄소 원자를 갖는, 알킬렌기 또는 치환된 알킬렌기를 나타내며; n은 1 내지 100의 범위의 정수이고; 그리고 X는 수소, 또는 -(CH₂)_a-SO₃M, -(CH₂)_b-COOM, -PO₃M₂, -P(Z)O₂M, 또는 -CO-CH₂-CH(SO₃M)-COOM(여기서, a 및 b는 각각 독립적으로 0 내지 4의 정수이며, Z는 화학식 (I)에서 X를 제거하여 수득된 잔기를 나타내며, 각각의 M은 수소, 알칼리 금속 원자, 알칼리 토금속 원자, 암모늄 잔기, 또는 알칸올아민 잔기를 나타냄)으로부터 선택되는 음이온 친수성기를 나타내는, 에멀젼 중합체; (B) 에멀젼 중합체의 건조 중량을 기준으로 1.1 고형 중량% 내지 20 고형 중량% 양의 왁스 에멀젼; 및 (C) 안료를 포함하는 수성 코팅 조성물로서, 상기 수성 코팅 조성물은 56% 내지 70%의 안료 부피 농도를 가지는, 수성 코팅 조성물이 제공된다. 본 수성 코팅 조성물은 높은 안료 부피 농도 (PVC), 개선된 비딩 효과 및 양호한 방오성을 제공한다.(A) An emulsion polymer comprising a structural unit of a polymerizable surfactant having the structure of formula (I),

(I)
Here, R ₁ is a phenyl group or a phenyl substituted alkyl group; m1 is 1, 2, 3 or 4; R ₂ is alkyl or substituted alkyl; m2 is 0 or 1; R ₃ is hydrogen or a C ₁ -C ₂₀ alkyl group; R ₄ is hydrogen or a C ₁ -C ₂₀ alkyl group; A represents an alkylene group or a substituted alkylene group having 2 to 4 carbon atoms; n is an integer ranging from 1 to 100; And X is hydrogen, or-(CH ₂ ) _a -SO ₃ M,-(CH ₂ ) _b -COOM, -PO ₃ M ₂ , -P (Z) O ₂ M, or -CO-CH ₂ -CH ( SO ₃ M) -COOM (where a and b are each independently an integer from 0 to 4, Z represents a residue obtained by removing X in formula (I), each M is hydrogen, an alkali metal atom, An emulsion polymer exhibiting an anionic hydrophilic group selected from alkali earth metal atoms, ammonium residues, or alkanolamine residues); (B) a wax emulsion in an amount of 1.1 to 20% by weight solids based on the dry weight of the emulsion polymer; And (C) as an aqueous coating composition comprising a pigment, wherein the aqueous coating composition has a pigment volume concentration of 56% to 70%, an aqueous coating composition is provided. The aqueous coating composition provides high pigment volume concentration (PVC), improved beading effect and good antifouling properties.

Description

Aqueous coating composition

The present invention relates to an aqueous coating composition and a method of improving the beading effect of a substrate by using it.

Beading effect (also known as “water repellency”) and antifouling properties are the main performance requirements for coating films. The beading effect is the resistance of the coating film to wetness, the resistance to adhesion of water on the coating film, and how easily water can be removed from the coating film.

In the coating industry, one of the commonly used and highly effective additives for repelling water is wax. The wax tends to migrate to the surface of the dry coating film, reducing the surface tension, thereby improving the beading effect. WO2015 / 051514A1 is based on the total dry weight of the coating composition in dry weight, i) as a polymerized unit, in dry weight based on the total dry weight of polymer particles, from 25% to 90% vinyl acetate; And 5% to 75% of polymer particles of 12% to 80%, including vinyl ester of versartic acid and / or vinyl ester of 2-ethyl hexanoic acid; And ii) 0.1% to 6% wax; And iii) 14% to 55% pigment. Such a coating composition with a pigment volume concentration (PVC) of 35.7% achieved improved liquid stain repellency. However, when the PVC of the coating composition increases higher than 55% (ie, a high PVC coating composition), the water repellency of the coating film needs to be further improved.

It is therefore desirable to provide a high PVC aqueous coating composition capable of providing coating films made from those having good antifouling properties as well as improved beading effects.

The present invention provides novel high PVC aqueous coating compositions by blending specific emulsion polymers, wax emulsions, and pigments. Aqueous coating compositions with high pigment volume concentrations (PVC), e.g. 56% or more, provide coatings with surprisingly improved beading effects with a beading score of 4 or higher and good antifouling properties with a stain removal score of 25 or higher. can do. Beading effect and antifouling properties can be measured according to the test methods described in the Examples section below.

In a first aspect, the present invention is an aqueous coating composition, the aqueous coating composition comprising:

(A) based on the dry weight of the emulsion polymer, an emulsion polymer comprising structural units of a polymerizable surfactant having the structure of formula (I):

(I)

(I)

Here, R ₁ is a phenyl group or a phenyl substituted alkyl group; m1 is 1, 2, 3 or 4; R ₂ is alkyl or substituted alkyl; m2 is 0 or 1; R ₃ is hydrogen or a C ₁ -C ₂₀ alkyl group; R ₄ is hydrogen or a C ₁ -C ₂₀ alkyl group; A represents an alkylene group or a substituted alkylene group having 2 to 4 carbon atoms, n is an integer ranging from 1 to 100, X is hydrogen, or-(CH ₂ ) _a -SO ₃ M,-( CH ₂ ) _b -COOM, -PO ₃ M ₂ , -P (Z) O ₂ M, or -CO-CH ₂ -CH (SO ₃ M) -COOM (where a and b are each independently 0-4 Is an integer, Z represents a residue obtained by removing X in formula (I), and each M is an anionic hydrophilic group selected from hydrogen, alkali metal atom, alkaline earth metal atom, ammonium residue, or alkanolamine residue) Emulsion polymer, which represents;

(B) a wax emulsion in an amount of 1.1 to 20% by weight solids based on the dry weight of the emulsion polymer; And

(C) contains a pigment,

Here, the aqueous coating composition has a pigment volume concentration of 56% to 70%.

In a second aspect, the present invention is a method of improving the beading effect of a substrate. The method is:

Forming an aqueous coating composition of the first aspect,

Applying the aqueous coating composition to a substrate, and

Drying or drying the aqueous coating composition, wherein the coated substrate has an improved beading effect.

“Acrylic” as used in the present invention includes (meth) acrylic acid, (meth) alkylacrylate, (meth) acrylamide, (meth) acrylonitrile and modified forms thereof, such as (meth) hydroxyalkyl acrylic Rate. Throughout this document, the word “(meth) acrylic” refers to both “methacryl” and “acrylic”. For example, (meth) acrylic acid represents both methacrylic acid and acrylic acid, and methyl (meth) acrylate represents both methyl methacrylate and methyl acrylate.

In the present invention, “glass transition temperature” or “T _g ” can be measured by various techniques including, for example, calculation using a differential scanning calorimeter (“DSC”) or Fox equation. The specific values of T _g reported herein were calculated using the Fox equation (TG Fox, Bull. Am. Physics Soc., Volume 1, Issue No. 3, page 123 (1956)). For example, for calculating the T _g of the copolymer of monomers M ₁ and M ₂ ,

,

,

Here, T _g (calc.) Is the glass transition temperature calculated for the copolymer, w (M ₁ ) is the weight fraction of the monomer M _{1 in} the copolymer, and w (M ₂ ) is the monomer M _{2 in} the copolymer. Weight fraction, T _g (M ₁ ) is the glass transition temperature of the homopolymer of monomer M ₁ , T _g (M ₂ ) is the glass transition temperature of the homopolymer of monomer M ₂ , and all temperatures are K. The glass transition temperature of the homopolymer can be found, for example, in "Polymer Handbook" (J. Brandrup and EH Immergut edited, Interscience Publishers).

The term “structural unit” of a named monomer, also known as a “polymerization unit”, refers to the remainder of the monomer after polymerization, ie, a polymerized monomer or a monomer in a polymerized form.

The aqueous coating composition of the present invention typically comprises an emulsion polymer present in the aqueous dispersion. Emulsion polymers useful in the present invention include structural units of one or more polymerizable surfactants. The polymerizable surfactant may have the structure of formula (I) below.

(I),

(I),

Here, R ₁ is a phenyl group or a phenyl substituted alkyl group;

m1 is 1, 2, 3 or 4, preferably 1 to 3;

R ₂ is alkyl or substituted alkyl, preferably C ₁ -C ₄ alkyl or substituted C ₁ -C ₄ alkyl;

m2 is 0 or 1, preferably 0;

R ₃ is hydrogen or a C ₁ -C ₂₀ or C ₁ -C ₄ alkyl group, for example methyl;

R ₄ is hydrogen or a C ₁ -C ₂₀ or C ₁ -C ₄ alkyl group, for example methyl;

A is an alkylene group having 2 to 4 carbon atoms or a substituted alkylene group such as ethylene, propylene, and butylene; Preferably, it represents an ethylene group;

n represents the average added mole number of alkylene oxide. n is 1 or more, 2 or more, 3 or more, 4 or more, or even 5 or more, and at the same time, 100 or less, 60 or less, 50 or less, 40 or less, or even 20 or less; Preferably, it is an integer from 5 to 20; And

X is hydrogen, or-(CH ₂ ) _a -SO ₃ M,-(CH ₂ ) _b -COOM, -PO ₃ M ₂ , -P (Z) O ₂ M, or -CO-CH ₂ -CH (SO ₃ M) -COOM (where a and b are each independently an integer from 0 to 4, Z represents a residue obtained by removing X from formula (I) above, and each M is hydrogen, an alkali metal atom, an alkali An anionic hydrophilic group selected from earth metal atoms, ammonium residues, or alkanolamine residues). Preferably, X represents -SO ₃ M.

In some embodiments, A is an ethylene group and n is an integer ranging from 5 to 20.

In one preferred embodiment, the polymerizable surfactant has the structure of formula (II).

(II)

(II)

Where R ₁ , m ₁ , and n are as defined above in formula (I), and M is a counter ion such as NH ₄ ⁺ , Li ⁺ , Na ⁺ or K ⁺ .

의 구조를 갖는 페닐 치환된 알킬기이며, 여기서, R은 1 내지 4개의 탄소 원자, 바람직하게는 2 내지 3개의 탄소 원자를 갖는 알킬렌기, 예를 들어,

,

, 또는

이다. 바람직한 m1은 3이다. 더 바람직하게는, 화학식 (II)에서, m1은 3이고; n은 5 내지 20의 범위인 정수이고; 그리고 R₁은

이다In formula (I) or (II), preferred R ₁ is

Is a phenyl substituted alkyl group having the structure of, wherein R is an alkylene group having 1 to 4 carbon atoms, preferably 2 to 3 carbon atoms, for example,

,

, or

to be. Preferred m1 is 3. More preferably, in formula (II), m1 is 3; n is an integer ranging from 5 to 20; And R ₁ is

to be

Suitable commercially available polymerizable surfactants include HITENOL AR-1025 alkylphenol polyethoxylate (APEO) free ethoxylated styrenated phenol sulfate polymerizable surfactants available from Dai-Ichi Kogyo Seiyaku Co., Ltd. do. Emulsion polymers useful in the present invention, based on the dry weight of the emulsion polymer, are 0.5 wt% or more, 0.75 wt% or more, 1.0 wt% or more, 1.1 wt% or more, 1.2 wt% or more, 1.3 wt% or more, or even 1.5 5% by weight or more, and at the same time, 5% by weight or less, 4.5% by weight or less, 4% by weight or less, 3.5% by weight or less, 3% by weight or less, 2.5% by weight or less, or It can even contain structural units of 2% by weight or less of a polymerizable surfactant.

Emulsion polymers useful in the present invention may further comprise structural units of one or more ethylenically unsaturated monomers (hereinafter referred to as "functional-group-containing ethylenically unsaturated monomers") carrying at least one functional group. The functional group can be selected from carbonyl, acetoacetoxy, acetoacetamide, ureido, amide, imide, amino, carboxyl, hydroxyl, or popularity. Examples of suitable additional functional-group-containing ethylenically unsaturated monomers include acid-supporting monomers such as α, β-ethylenically unsaturated carboxylic acids including methacrylic acid, acrylic acid, itaconic acid, maleic acid, or fumaric acid; Or monomers that produce acidic groups such as anhydride, (meth) acrylic anhydride, or maleic anhydride or carry acid-forming groups that can be subsequently converted; Acetoacetoxyethyl methacrylate (AAEM); Vinyl phosphonic acid, allyl phosphonic acid, phosphoalkyl (meth) acrylates such as phosphoethyl (meth) acrylate, phosphopropyl (meth) acrylate, phosphobutyl (meth) acrylate, or salts thereof; 2-acrylamido-2-methyl-1-propanesulfonic acid; Sodium salt of 2-acrylamido-2-methyl-1-propanesulfonic acid; Ammonium salt of 2-acrylamido-2-methyl-1-propane sulfonic acid; Sodium styrene sulfonate; Sodium vinyl sulfonate; Sodium salt of allyl ether sulfonate; Etc; Diacetone acrylamide (DAAM), acrylamide, methacrylamide, mono-substituted (meth) acrylamide, N-methylacrylamide, N-ethylacrylamide, N-isopropylacrylamide, N-butylacrylamide, N -Tertiary butylacrylamide, N-2-ethylhexylacrylamide, N, N-dimethylacrylamide, N, N-diethylacrylamide, methylacrylamidoethyl ethylene urea, hydroxy-functional (meth) acrylic acid alkyl ester For example hydroxyethyl methacrylate and hydroxypropyl methacrylate, or mixtures thereof. Preferred functional-group-containing ethylenically unsaturated monomers are selected from acrylic acid, methacrylic acid, acrylamide, sodium p-styrene sulfonate, or mixtures thereof. Emulsion polymers will comprise from 0.3% to 20% by weight, from 0.5% to 10% by weight, or from 1.0% to 8.0% by weight of functional-group-containing ethylenically unsaturated monomer structural units, based on the dry weight of the emulsion polymer. You can.

Emulsion polymers useful in the present invention may also include structural units of at least one ethylenically unsaturated nonionic monomer different from the functional-group-containing ethylenically unsaturated monomer. As used herein, the term "nonionic monomer" refers to a monomer that does not have an ionic charge at pH = 1-14. Suitable ethylenically unsaturated nonionic monomers are, for example, alkyl esters of (methyl) acrylic acid such as methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, decyl acrylate, lauryl acrylate, methyl Monoethylenically unsaturated nonionic monomers including methacrylate, butyl methacrylate, isodecyl methacrylate, lauryl methacrylate, (meth) acrylonitrile, or mixtures thereof. Preferably, the ethylenically unsaturated nonionic monomer is selected from the group consisting of methyl methacrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate and styrene. The emulsion polymer may comprise 71% to 97.7% by weight or 83% to 97% by weight of the structural unit of the ethylenically unsaturated nonionic monomer, based on the dry weight of the emulsion polymer.

In some embodiments, the emulsion polymer, based on the dry weight of the emulsion polymer,

1 wt% to 3 wt% of the structural unit of the polymerizable surfactant,

Structural units of ethylenically unsaturated monomers carrying 1% to 6% of at least one functional group;

30% to 55% by weight of structural units of styrene; And

Structural units of 36% to 68% by weight of an alkyl ester of (methyl) acrylic acid such as methyl methacrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, or mixtures thereof.

Emulsion polymers useful in the present invention can be prepared by emulsion polymerization of a mixture of the above-mentioned polymerizable surfactants and monomers comprising other monomers. The total weight concentration of the above polymerizable surfactant and other monomers for preparing the emulsion polymer is 100%. The mixture of monomers can be added purely or in water as an emulsion; Or one or more additions over the course of the reaction to produce the emulsion polymer, or continuously, linearly or nonlinearly. Suitable temperatures for the emulsion polymerization process may be less than 100 ° C, in the range of 30 ° C to 95 ° C, or in the range of 50 ° C to 90 ° C.

In the polymerization process for the preparation of emulsion polymers, free radical initiators can be used. The polymerization process can be thermal initiated or redox initiated emulsion polymerization. Examples of suitable free radical initiators include hydrogen peroxide, t-butyl hydroperoxide, cumene hydroperoxide, ammonium and / or alkali metal persulfate, sodium perborate, superphosphoric acid and salts thereof; Potassium permanganate, and ammonium or alkali metal salts of disulfide peroxide. The free radical initiator may be used at a level of 0.01 to 3.0% by weight, typically based on the total weight of the monomers. Redox systems comprising the aforementioned initiators coupled with suitable reducing agents can be used in the polymerization process. Examples of suitable reducing agents are sodium sulfoxylate formaldehyde, ascorbic acid, isoascorbic acid, alkali metal and ammonium salts of sulfur-containing acids such as sodium sulfite, bisulfite, thiosulfate, hydrosulfite, sulfide, hydrosulfide or Dithionite, formadinsulfonic acid, acetone bisulfite, glycolic acid, hydroxymethanesulfonic acid, glyoxylic acid hydrate, lactic acid, glyceric acid, malic acid, tartaric acid and salts of the preceding acid. Metal salts of iron, copper, manganese, silver, platinum, vanadium, nickel, chromium, palladium or cobalt can be used to catalyze the redox reaction. Metal chelating agents can be optionally used.

In the polymerization process for the preparation of emulsion polymers, one or more additional surfactants can be used. The additional surfactant is different from the above polymerizable surfactant having the structure of formula (I). Additional surfactants can be added prior to or during the polymerization of the monomers, or a combination thereof. Some of the additional surfactants can also be added after polymerization. These additional surfactants may include anionic and / or nonionic emulsifiers. Examples of suitable additional surfactants are RHODAFAC RS-610 alkyl ethoxylated phosphate available from Solvay SA, DISPONIL FES 32 fatty alcohol ether sulfate available from BASF, TERGITOL ™ 15-S-40 secondary alcohol available from Dow Chemical Company Ethoxylate (TERGITOL is a trademark of The Dow Chemical Company). The additional surfactant used is generally 0 to 3%, 0.5% to 2.5%, or 0.7% to 1.5% by weight, based on the weight of the monomer mixture used to prepare the emulsion polymer.

In the polymerization process to produce emulsion polymers, chain transfer agents can be used. Examples of suitable chain transfer agents are 3-mercaptopropionic acid, n-dodecyl mercaptan, methyl 3-mercaptopropionate, butyl 3-mercaptopropionate, benzenethiol, azelaic alkyl mercaptan , Or mixtures thereof. Chain transfer agents can be used in an amount effective to control the molecular weight of the emulsion polymer. The chain transfer agent can be used in an amount of 0 to 1% by weight, 0.1% to 0.5% by weight, or 0.15% to 0.4% by weight based on the weight of the monomer mixture used to prepare the emulsion polymer.

After completing the polymerization of the emulsion polymer, the resulting emulsion polymer can be neutralized with one or more bases as neutralizing agents, for example to a pH value of at least 6, or 6 to 10, or 7 to 9. The base can result in partial or complete neutralization of the ionic groups or latently ionic groups of the emulsion polymer. Examples of suitable bases include ammonia; Alkali metal or alkaline earth metal compounds such as sodium hydroxide, potassium hydroxide, calcium hydroxide, zinc oxide, magnesium oxide, sodium carbonate; Primary, secondary and tertiary amines such as triethyl amine, ethylamine, propylamine, monoisopropylamine, monobutylamine, hexylamine, ethanolamine, diethyl amine, dimethyl amine, tributylamine, triethanolamine, Dimethoxyethylamine, 2-ethoxyethylamine, 3-ethoxypropylamine, dimethylethanolamine, diisopropanolamine, morpholine, ethylenediamine, 2-diethylaminoethylamine, 2,3-diaminopropane, 1 , 2-propylenediamine, neopentanediamine, dimethylaminopropylamine, hexamethylenediamine, 4,9-dioxadodecane-1,12-diamine, polyethyleneimine or polyvinylamine; Aluminum hydroxide; Or mixtures thereof.

Emulsion polymers useful in the present invention have an average particle size of 50 nanometers (nm) to 500 nm, 80 nm to 200 nm, or 90 nm to 150 nm, as measured by a Brookhaven BI-90 or 90Plus particle size meter. You can.

The aqueous coating composition of the present invention may further include one or more wax emulsions. The wax emulsion can be a polyethylene (PE) wax, such as high density polyethylene (HDPE) wax, polypropylene (PP) wax, carnauba wax, paraffin wax, polyethylene acrylic acid wax, or mixtures thereof. Suitable commercially available wax emulsions are, for example, MICHEM ME 62330 paraffin / PE wax emulsion, MICHEM ME 34935 paraffin / ethylene acrylic acid wax emulsion, a blend of MICHEM 180 paraffin and carnauba wax, all available from Michelman Inc. , And MICHEM ME 71450 paraffin wax emulsion; Both ULTRALUBE E340 paraffin wax emulsion and ULTRALUBE E668H PP wax emulsion available from Keim-Additec; Or mixtures thereof.

In one embodiment, paraffin wax emulsions are used. Preferably, the paraffin wax emulsion is a melt purified paraffin wax, or a blend of other materials. Paraffin wax typically has a melting temperature of 46 ° C to 71 ° C. The solids of the paraffin wax emulsion may vary from 1% to 60% by weight, or 30% to 55% by weight. The pH of the wax emulsion can range from 6 to 10, typically 7.9 to 9.8, but depends on the process used. The particle size of the paraffin wax emulsion can vary from 0.02 to 1.5 microns. Paraffin wax emulsions can be prepared by melting purified paraffin wax to a temperature above the melting point of paraffin. Suitable emulsifiers such as stearic acid, oleic acid, diethylamine ethanol, 2-amino-2-methyl-1-propanol can be added slowly to the molten wax and water mixture with stirring at elevated temperature. Subsequently, a base, such as potassium hydroxide or ammonium hydroxide, is dissolved in ethylene glycol or water at elevated temperature and can be added to the resulting mixture with increasing stirring speed. After all the water / base mixture is added to the molten wax, the wax in the resulting water emulsion can be passed through a homogenizer to further adjust the particle size of the wax emulsion. After homogenization, the resulting wax emulsion is cooled, for example through a heat exchanger, after which it is filtered and packaged.

Wax emulsions useful in the present invention can have an average particle size of 10 nm to 1,000 nm, 30 nm to 500 nm, 50 nm to 200 nm as measured by a Brookhaven BI-90 or 90Plus particle sizer. The aqueous coating composition of the present invention is 1.1% or more, 1.2% or more, 1.5% or more, 1.6% or more, 1.7% or more, 1.8% or more, 1.9% or more, 2% or more by solid weight based on the dry weight of the emulsion polymer, 2.5% or more, or even 3% or more, and at the same time, 20% or less, 18% or less, 15% or less, 10% or less, 8% or less, 6% or less, 5.5 % Or less, 5% or less, 4.5% or less, or even 4% or less of a wax emulsion.

The aqueous coating composition of the present invention may also include one or more pigments. As used herein, the term "pigment" refers to a particulate inorganic material that can substantially contribute to the opacity or hiding capability of the coating. Such materials typically have a refractive index greater than 1.8 and include inorganic and organic pigments. Examples of suitable inorganic pigments are titanium dioxide (TiO ₂ ), zinc oxide, zinc sulfide, iron oxide, barium sulfate, barium carbonate or mixtures thereof. The preferred pigment used in the present invention is TiO ₂ . TiO ₂ may also be available in the form of concentrated dispersions.

The aqueous coating composition of the present invention may also include one or more extenders. The term "extender" refers to particulate inorganic materials having a refractive index greater than 1.3 and up to 1.8. Examples of suitable bulking agents include calcium carbonate, aluminum oxide (Al ₂ O ₃ ), clay, calcium sulfate, aluminosilicate, silicate, zeolite, mica, diatomaceous earth, solid or hollow glass, ceramic beads and opaque polymers such as The ROPAQUE ™ Ultra E, available from Dow Chemical Company (ROPAQUE is a trademark of The Dow Chemical Company), or mixtures thereof.

The aqueous coating composition of the present invention is 56% or more, 57% or more, 58% or more, 59% or more, or even 60% or more, and at the same time, 70% or less, 69% or less, 68% or less, Pigment volume concentrations (PVC) of 67% or less, 66% or less, or even 65% or less. The PVC of the coating composition can be determined according to the following equation:

The aqueous coating composition of the present invention may further include one or more anti-foaming agents. “Antifoaming agent” as used herein refers to a chemical additive that reduces and interferes with the formation of foam. The antifoaming agent may be a silicone-based antifoaming agent, a mineral oil-based antifoaming agent, an ethylene oxide / propylene oxide-based antifoaming agent, or a mixture thereof. Suitable commercially available antifoaming agents include, for example, TEGO Airex 902 W and TEGO Foamex 1488 polyether siloxane copolymer emulsions both available from TEGO, BYK-024 silicone antifoaming agents available from BYK or mixtures thereof. The anti-foaming agent may be present in an amount of generally 0 to 0.5%, 0.05% to 0.4%, or 0.1% to 0.3% by weight based on the total weight of the aqueous coating composition.

The aqueous coating composition of the present invention may further include one or more thickeners, also known as “rheology modifiers”. Thickeners can include polyvinyl alcohol (PVA), acid derivatives, acid copolymers, urethane associative thickeners (UAT), polyether urea polyurethanes (PEUPU), polyether polyurethanes (PEPU), or mixtures thereof. Examples of suitable thickeners include alkali swellable emulsions (ASE), such as sodium or ammonium neutralized acrylic acid polymers; Hydrophobically modified alkali swellable emulsions (HASE), such as hydrophobically modified acrylic acid copolymers; Associative thickeners, such as hydrophobically modified ethoxylated urethanes (HEUR); And cellulose thickeners such as methyl cellulose ether, hydroxymethyl cellulose (HMC), hydroxyethyl cellulose (HEC), hydrophobically-modified hydroxy ethyl cellulose (HMHEC), sodium carboxymethyl cellulose (SCMC), sodium carboxymethyl 2-hydroxyethyl cellulose, 2-hydroxypropyl methyl cellulose, 2-hydroxyethyl methyl cellulose, 2-hydroxybutyl methyl cellulose, 2-hydroxyethyl ethyl cellulose, and 2-hydroxypropyl cellulose. Preferably, the thickener is selected from HASE, HEC, HEUR, or mixtures thereof. The thickener may be present in an amount of 0% to 3.0% by weight, 0.1% to 1.5% by weight, or 0.2% to 1.2% by weight, based on the total weight of the aqueous coating composition.

The aqueous coating composition of the present invention may further include one or more humectants. As used herein, “wetting agent” refers to a chemical additive that reduces the surface tension of the coating composition, which makes the coating composition more easily diffuse or penetrate across the surface of the substrate. Wetting agents can be polycarboxylate, anionic, amphoteric or nonionic. Suitable commercially available wetting agents are, for example, TRITON ^™ CF-10 nonionic surfactants available from The Dow Chemical Company (TRITON is a trademark of The Dow Chemical Company), actacetylene diol available from Air Products. SURFYNOL 10 based nonionic wetting agents, both include BYK-346 and BYK-349 polyether-modified siloxanes available from BYK, or mixtures thereof. Wetting agents may be present in an amount of 0% to 1.0%, 0.1% to 0.8%, or 0.2% to 0.6% by weight, based on the total weight of the aqueous coating composition.

The aqueous coating composition of the present invention may further include one or more adhesives. “Adhesive” herein refers to a slow-evaporating solvent that fuses polymer particles into a continuous film under ambient conditions. Examples of suitable coalescing agents are 2-n-butoxyethanol, dipropylene glycol n-butyl ether, propylene glycol n-butyl ether, dipropylene glycol methyl ether, propylene glycol methyl ether, propylene glycol n-propyl ether, diethylene Glycol monobutyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, triethylene glycol monobutyl ether, dipropylene glycol n-propyl ether, n-butyl ether or mixtures thereof. Preferred coalescents are TEXANOL ester alcohols available from Eastman Chemical Company, Coasol and Coasol 290 plus coalescents available from Chemoxy International Ltd., dipropylene glycol n-butyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, n-butyl ether, or mixtures thereof. The coalescing agent may be present in an amount of 0% to 3.0% by weight, 0.1% to 2.0% by weight, or 0.2% to 1.5% by weight, based on the total weight of the aqueous coating composition.

The aqueous coating composition of the present invention may further include one or more dispersants. Dispersants are non-ionic, anionic and cationic dispersants, such as polyacids of suitable molecular weight, 2-amino-2-methyl-1-propanol (AMP), dimethyl amino ethanol (DMAE), potassium tripolyphosphate ( KTPP), trisodium polyphosphate (TSPP), citric acid and other carboxylic acids. The polyacids used are hydrophobicly- or hydrophilically-modified ones, such as polyacrylic acid or with various monomers such as styrene, acrylate or methacrylate esters, diisobutylene, and other hydrophilic or hydrophobic comonomers. Homopolymers and copolymers based on polycarboxylic acids, including polymethacrylic acid or maleic anhydride; Salts thereof; Or mixtures thereof. The molecular weight of these polyacids is gel permeation chromatography (GPC) (column: One PLgel GUARD column (10 μm, 50 × 7.5 mm) and One Mixed B column (7.8 × 300 mm); and calibration: polynom 3 1,000 to 50,000, 1,200 to 40,000, 1,500 to 20,000, 2,000 to 15,000, or 2,500 to 10,000, as measured by PL polystyrene narrow standards with molecular weights ranging from 2329000 to 580 g / mol using fitness) It can be a range of. The dispersant may be present in an amount of 0% to 1.0% by weight, 0.1% to 0.8% by weight, or 0.2% to 0.6% by weight, based on the total weight of the aqueous coating composition.

In addition to the above components, the aqueous coating composition of the present invention may further include any one or a combination of the following additives: buffer, neutralizing agent, moisturizing agent, mildewcide, biocide, anti-film agent ( anti-skinning agents, colorants, flow agents, crosslinking agents, antioxidants, plasticizers, leveling agents, thixotropic agents, adhesion promoters and grind vehicles. If these additives are present, they may be present in a combined amount of 0% to 1% by weight, or 0.1% to 0.8% by weight, based on the total weight of the aqueous coating composition.

The aqueous coating composition of the present invention may further include water. The concentration of water can be 30% to 90%, 40% to 80%, or 50% to 70%, based on the total weight of the aqueous coating composition.

 The aqueous coating composition of the present invention can be prepared by mixing an emulsion polymer, a wax emulsion, a pigment, and optionally other components described above. The components in the aqueous coating composition can be mixed in any order to provide the aqueous coating composition of the present invention. Any of the optional components mentioned above can also be added to the composition during or prior to mixing to form the aqueous coating composition. The pigment and / or extender is preferably mixed with a dispersant to form a slurry of the pigment and / or extender.

The aqueous coating composition of the present invention has excellent heat-aging stability, e.g., the change in the medium shear viscosity of the aqueous coating composition is 10 days or more, or up to 30 days, as measured by the Stormer Viscosity Meter according to ASTM D562 method. Less than 10 Krebs units (KU) after storage at 50 ° C.

The aqueous coating compositions of the present invention can be used even when the aqueous coating composition has PVC as high as 56% or more, 57% or more, or even 58% or more (also called "high PVC aqueous coating composition"). It is possible to provide a good beading effect to the coating obtained from. As used herein, "good beading effect" or "improved beading effect" refers to a coated or coated substrate that achieves a 4 or higher beading effect score. The aqueous coating composition can also provide the coating with good antifouling properties as indicated by a 25 or higher stain removal score. Beading effect and antifouling properties can be measured according to the test methods described in the Examples section below.

The present invention also relates to a method of improving the beading effect of a substrate. The method includes the following steps: forming an aqueous coating composition, applying the aqueous coating composition to a substrate, and drying or allowing the aqueous coating composition to dry, wherein the substrate is the Step, with improved beading effect as described in. The step of drying or allowing the applied aqueous coating composition to dry forms a coating. The present aqueous coating composition can be applied and attached to various substrates. Suitable substrates include wood, metal, foam, rock, elastomeric substrates, glass, wallpaper, fabric, medium-density fiberboard (MDF), particle board, gypsum board, concrete or cementitious There is a substrate. The aqueous coating composition can be applied to the substrate by existing means including brushing, dipping, rolling and spraying. The aqueous composition is preferably applied by spraying. Standard spraying techniques and equipment for spraying can be used, for example air-atomic spraying, air spraying, airless spraying, high capacity low pressure spraying and electrostatic spraying, such as electrostatic bell application, and manual or automatic methods. After the aqueous coating composition is applied to the substrate, the coating composition can be dried or dried at room temperature (20 ° C. to 25 ° C.) or at elevated temperatures, such as 35 ° C. to 60 ° C. to form a film (ie coating). have. The coating composition may be used alone or in combination with other coatings to form a multilayer coating.

The aqueous coating compositions of the present invention are useful as coatings on a variety of substrates, such as those routinely exposed outdoors, where good beading effects and good antifouling properties are important. Aqueous coating compositions can be used in a variety of applications, such as marine and protective coatings, automotive coatings, road marking paints, exterior insulation and finish systems (EIFS), roof mastic, wood coatings, coil coatings, plastics Suitable for coatings, powder coatings, can coatings, architectural coatings, and civil coatings. The aqueous coating composition is particularly useful for architectural coatings.

Example

Some embodiments of the present invention will now be described in the following examples, where all parts and percentages are by weight unless otherwise specified.

Styrene ("ST"), butyl acrylate ("BA"), sodium styrene sulfonate ("SSS"), and acrylic acid ("AA") are all available from The Dow Chemical Company.

HITENOL AR-1025 ("AR-1025") surfactant (25% active) available from Dai-Ichi Kogyo Seiyaku Co., Ltd. is an APEO free polyoxyethylene styrenated tri-propenyl phenyl ether sulfate ammonium salt .

ADEKA REASOAP PP-7025 ("PP-7025") surfactant (25% active) available from ADEKA (Shanghai) Co., Ltd. is α- (2-propenyloxy) -ω-hydroxy-poly (propylene Oxide) phosphate.

The MAXEMUL 6112 reactive surfactant available from Croda is a vinyl alkyl phosphate ester.

ADEKA REASOAP SR-10 ("SR-10") reactive surfactant (25% active) available from ADEKA (Shanghai) Co., Ltd. is an anionic polymerizable emulsifier, poly (oxy-1,2-ethanediyl) , Alpha-sulfo-omega-1- (hydroxymethyl) -2- (2-propenyloxy) ethoxy]-, alkyl ether ammonium salt.

The RHODACAL DS-4 ("DS-4") surfactant (22% active) available from Rhodia (China) Investment Co., Ltd. is sodium dodecyl (branched) benzene sulfonate.

ULTRALUBE E-340 ("E-340") wax emulsion available from Keim-Additec Company is a paraffin wax emulsion with a solids content of 50%.

NATROSOL 250 HBR Hydroxyethyl Cellulose (HEC), available from Ashland Company, is used as a thickener.

AMP-95, available from Angus Company, is used as a neutralizing agent.

Propylene glycol is available from Sinopharm Chemical Reagent Co., Ltd.

OROTAN ^TM 731A dispersant, KATHON ^TM LXE biocide, ROPAQUE Ultra E opaque polymer, TRITON CF-10 wetting agent, ACRYSOL ^TM RM-2020 NPR HEUR thickener, ACRYSOL ASE-60 HASE thickener and ACRYSOL RM-8W HEUR thickener are all available from The Dow Chemical Company (OROTAN, KATHON and ACRYSOL All are trademarks of The Dow Chemical Company).

NOPCO NXZ antifoam is available from San Nopco Ltd.

Ti-Pure R-706 titanium dioxide, available from DuPont Company, is used as the pigment.

CC-700 calcium deoxidizer, available from Guangfu Building Materials Group, is used as a bulking agent.

TEXANOL ester alcohol, available from Eastman Chemical Company, is used as an adhesive.

The following standard analytical devices and methods are used in the examples.

Beading effect evaluation

The beading effect evaluates the difficulty of wetting the coating surface with water. To determine the beading effect, the test coating composition was cast on a black vinyl chart P-121-10N (Reneta) and dried at room temperature (20-25 ° C) for 2 days. The coated chart was kept vertical so that water droplets flowed from the top of the chart to the bottom. The beading effect was visually graded and expressed as a beading score as shown in Table 1 below. A bead score of 4 or higher shows a good beading effect. Otherwise, if the beading score is lower than 4, this shows a poor beading effect.

Antifouling

The antifouling properties of the coating were evaluated according to the ASTM D4828-94 method. The test coating composition was coated on a black vinyl chart P-121-10N (Reneta) with a wet thickness of 175 μm and dried in a constant temperature room (CTR, 25 ° C., 50% relative humidity (R.H.)) for 7 days. Hydrophobic stains including lipstick, pencil, ballpoint pen, crayon (blue), crayon (green), and crayon (pink), respectively, were applied to the surface of the coating, respectively. Hydrophilic stains, each including red wine, coffee, black tea, green tea, and ink were applied by placing gauze saturated with stains corresponding to the surface of the coating and held on the surface for 2 hours. Before the antifouling test, excess liquid stains were wiped off with a paper towel. Thereafter, an antifouling test was performed on a modified scrub machine with a boat filled with a 3M commercial sponge saturated with 1% household detergent solution. One kilogram (Kg) weight was placed on the boat to ensure that all samples were tested under the same pressure. Each sample chart was scrubbed for 100 cycles. Before ranking the antifouling performance, the sample chart was rinsed with water, followed by complete drying at room temperature. The antifouling performance of the coating was then evaluated by visual inspection by comparing the scrubbed side with the unscrubbed side, based on the standards listed in Table 2.

The antifouling properties of these coatings were evaluated using the sum of the stain removal scores for the different tested stains for each coating. The sum of 25 or higher stain removal scores shows good antifouling properties. Otherwise, if the sum of stain removal scores is less than 25, it indicates that the coating is poor in antifouling properties. The higher the sum of stain removal scores, the better the antifouling properties of the coating.

Synthesis of Binder 1A-1F

Monomer emulsion (ME) was prepared by mixing 400 g of deionized (DI) water, 69 g of HITENOL AR-1025, 718.50 g of ST, 754.46 g of BA, 5.52 g of SSS, and 30.5 g of AA Did.

To a 5-liter 4-neck round bottom flask, equipped with a paddle stirrer, thermometer, nitrogen inlet and reflux condenser, 510 g of deionized water was added and heated to 90 ° C. while stirring under a nitrogen atmosphere. 8.50 g of DS-4, 1.87 g of Na ₂ CO ₃ , and 51.7 g of ME were then added to the flask, followed by 5.25 g of sodium persulfate dissolved in 14.7 g of deionized water. The batch was kept agitated for 1 minute and co-feed of 2.12 g of sodium persulfate in 50 g of deionized water and 2.30 g of sodium hydrogen sulfite in 50 g of deionized water within 120 minutes while adding the remaining ME to the flask. . When the ME feed is complete, a catalyst / active agent feed (1.40 g tert-butyl hydroperoxide / 0.7 g iso-ascorbic acid) is added, followed by another catalyst / active agent feed (3 g tert- Butyl hydroperoxide / 1.6 g of iso-ascorbic acid) was added to the flask in 40 minutes to separate the remaining monomers. Then, a monoethanolamine (MEA) solution was added to adjust the pH to 8.0-8.5. Finally, various amounts of E340 wax emulsion as provided in the table below were slowly added after. The measured particle size of each binder composition was about 135 nm and the solids content was about 50.90%.

Synthesis of Binder 2

The monomer emulsion (ME) was prepared by mixing 400 g of deionized water, 68.7 g DS-4, 718.50 g ST, 754.46 g BA, 5.52 g SSS, and 30.5 g AA.

To a 5-liter 4-neck round bottom flask, equipped with a paddle stirrer, thermometer, nitrogen inlet and reflux condenser, 510 g of deionized water was added and heated to 90 ° C. while stirring under a nitrogen atmosphere. 8.50 g of DS-4, 1.87 g of Na ₂ CO ₃ , and 51.7 g of ME were then added to the flask, followed by 5.25 g of sodium persulfate dissolved in 14.7 g of deionized water. The batch was kept agitated for 1 minute and the ME was added to the flask while co-feeding 2.12 g of sodium persulfate in 50 g of deionized water and 2.30 g of sodium hydrogen sulfite in 50 g of deionized water within 120 minutes. When the ME feed is complete, a catalyst / active agent feed (1.40 g tert-butyl hydroperoxide / 0.7 g iso-ascorbic acid) is added, followed by another catalyst / active agent feed (3 g tert- Butyl hydroperoxide / 1.6 g of iso-ascorbic acid) was added to the flask in 40 minutes to separate the remaining monomers. Then the pH was adjusted to 8.0-8.5 by adding MEA solution. Finally, 186.5 g of E340 wax emulsion was added slowly after. The measured particle size of the obtained binder composition was about 150 nm and the solids content was about 50.90%.

Synthesis of Binder 3

The monomer emulsion (ME) was prepared by mixing 400 g deionized water, 69 g ADEKA REASOAP PP-7025, 718.50 g ST, 754.46 g BA, 5.52 g SSS, and 30.5 g AA.

To a 5-liter 4-neck round bottom flask, equipped with a paddle stirrer, thermometer, nitrogen inlet and reflux condenser, 510 g of deionized water was added and heated to 90 ° C. while stirring under a nitrogen atmosphere. 8.50 g of DS-4, 1.87 g of Na ₂ CO ₃ , and 51.7 g of ME were then added to the flask, followed by 5.25 g of sodium persulfate dissolved in 14.7 g of deionized water. The batch was kept agitated for 1 minute and co-feed of 2.12 g of sodium persulfate in 50 g of deionized water and 2.30 g of sodium hydrogen sulfite in 50 g of deionized water within 120 minutes while adding the remaining ME to the flask. . When the ME feed is complete, a catalyst / active agent feed (1.40 g tert-butyl hydroperoxide / 0.7 g iso-ascorbic acid) is added, followed by another catalyst / active agent feed (3 g tert- Butyl hydroperoxide / 1.6 g of iso-ascorbic acid) was added to the flask in 40 minutes to separate the remaining monomers. Then the pH was adjusted to 8.0-8.5 by adding MEA solution. Finally, 186.5 g of E340 wax emulsion was added slowly after. The measured particle size of the obtained binder composition was about 170 nm and solids content was about 51.90%.

Synthesis of Binder 4

The monomer emulsion (ME) was prepared by mixing 400 g deionized water, 69 g MAXEMUL 6112, 718.50 g ST, 754.46 g BA, 5.52 g SSS, and 30.5 g AA.

To a 5-liter 4-neck round bottom flask, equipped with a paddle stirrer, thermometer, nitrogen inlet and reflux condenser, 510 g of deionized water was added and heated to 90 ° C. while stirring under a nitrogen atmosphere. 8.50 g of DS-4, 1.87 g of Na ₂ CO ₃ , and 51.7 g of ME were then added to the flask, followed by 5.25 g of sodium persulfate dissolved in 14.7 g of deionized water. The batch was kept agitated for 1 minute and co-feed of 2.12 g of sodium persulfate in 50 g of deionized water and 2.30 g of sodium hydrogen sulfite in 50 g of deionized water within 120 minutes while adding the remaining ME to the flask. . When the ME feed is complete, a catalyst / active agent feed (1.40 g tert-butyl hydroperoxide / 0.7 g iso-ascorbic acid) is added, followed by another catalyst / active agent feed (3 g tert- Butyl hydroperoxide / 1.6 g of iso-ascorbic acid) was added to the flask in 40 minutes to separate the remaining monomers. Then the pH was adjusted to 8.0-8.5 by adding MEA solution. Finally, 186.5 g of E340 wax emulsion was added slowly after. The measured particle size of the obtained binder composition was about 150 nm and the solids content was about 52.35%.

Synthesis of Binder 5

The monomer emulsion (ME) was prepared by mixing 400 g deionized water, 69 g ADEKA REASOAP SR-10, 718.50 g ST, 754.46 g BA, 5.52 g SSS, and 30.5 g AA.

To a 5-liter 4-neck round bottom flask, equipped with a paddle stirrer, thermometer, nitrogen inlet and reflux condenser, 510 g of deionized water was added and heated to 90 ° C. while stirring under a nitrogen atmosphere. 8.50 g of DS-4, 1.87 g of Na ₂ CO ₃ , and 51.7 g of ME were then added to the flask, followed by 5.25 g of sodium persulfate dissolved in 14.7 g of deionized water. The batch was kept agitated for 1 minute and co-feed of 2.12 g of sodium persulfate in 50 g of deionized water and 2.30 g of sodium hydrogen sulfite in 50 g of deionized water within 120 minutes while adding the remaining ME to the flask. . When the ME feed is complete, a catalyst / active agent feed (1.40 g tert-butyl hydroperoxide / 0.7 g iso-ascorbic acid) is added, followed by another catalyst / active agent feed (3 g tert- Butyl hydroperoxide / 1.6 g of iso-ascorbic acid) was added to the flask in 40 minutes to separate the remaining monomers. Then the pH was adjusted to 8.0-8.5 by adding MEA solution. Finally, 186.5 g of E340 wax emulsion was added slowly after. The measured particle size of the obtained binder composition was about 150 nm and the solids content was about 52.41%.

Synthesis of Binder 6

The monomer emulsion (ME) was prepared by mixing 400 g deionized water, 69 g HITENOL AR-1025, 718.50 g ST, 754.46 g BA, 5.52 g SSS, and 30.5 g AA.

To a 5-liter 4-neck round bottom flask, equipped with a paddle stirrer, thermometer, nitrogen inlet and reflux condenser, 510 g of deionized water was added and heated to 90 ° C. while stirring under a nitrogen atmosphere. 8.50 g of DS-4, 1.87 g of Na ₂ CO ₃ , and 51.7 g of ME were then added to the flask, followed by 5.25 g of sodium persulfate dissolved in 14.7 g of deionized water. The batch was kept agitated for 1 minute and co-feed of 2.12 g of sodium persulfate in 50 g of deionized water and 2.30 g of sodium hydrogen sulfite in 50 g of deionized water within 120 minutes while adding the remaining ME to the flask. . When the ME feed is complete, a catalyst / active agent feed (1.40 g tert-butyl hydroperoxide / 0.7 g iso-ascorbic acid) is added, followed by another catalyst / active agent feed (3 g tert- Butyl hydroperoxide / 1.6 g of iso-ascorbic acid) was added to the flask in 40 minutes to separate the remaining monomers. Then the pH was adjusted to 8.0-8.5 by adding MEA solution. The measured particle size of the obtained binder composition was about 120 nm and solids content was about 50.00%.

Synthesis process of binder 7

The monomer emulsion (ME) was prepared by mixing 400 g of deionized (DI) water, 68.7 g DS-4, 718.50 g ST, 754.46 g BA, 5.52 g SSS, and 30.5 g AA. .

To a 5-liter 4-neck round bottom flask, equipped with a paddle stirrer, thermometer, nitrogen inlet and reflux condenser, 510 g of deionized water was added and heated to 90 ° C. while stirring under a nitrogen atmosphere. 8.50 g of DS-4, 1.87 g of Na ₂ CO ₃ , and 51.7 g of ME were then added to the flask, followed by 5.25 g of sodium persulfate dissolved in 14.7 g of deionized water. The batch was kept agitated for 1 minute and co-feed of 2.12 g of sodium persulfate in 50 g of deionized water and 2.30 g of sodium hydrogen sulfite in 50 g of deionized water within 120 minutes while adding the remaining ME to the flask. . When the ME feed is complete, a catalyst / active agent feed (1.40 g tert-butyl hydroperoxide / 0.7 g iso-ascorbic acid) is added, followed by another catalyst / active agent feed (3 g tert- Butyl hydroperoxide / 1.6 g of iso-ascorbic acid) was added to the flask in 40 minutes to separate the remaining monomers. Then the pH was adjusted to 8.0-8.5 by adding MEA solution. The measured particle size of the obtained binder composition was about 180 nm and the solids content was about 50.00%.

The obtained binder composition was used together with different PVC to prepare the following coating composition.

Example (Ex) 1-10 and Comparative (Comp) Ex A-D and G coating compositions

Coating compositions with 60% PVC (Ex 1-5, and Comp Ex A-D and G) were prepared based on the formulations listed in Table 3. The binder composition as prepared was used to prepare each coating composition according to the formulation provided in Table 6. The ingredients for grinding were mixed using a high-speed Cowles disperser. Thereafter, the component for letdown was added and mixed with a conventional stirrer.

Ex 6-9 and Comp Ex H coating compositions

Coating compositions with other PVC, such as 58% (Ex 6), 60% (Ex 7), 65% (Ex 8), 68% (Ex 9) and 71% (Comp Ex H), are also 60% Obtained based on the procedure and formulation for preparing PVC coating compositions such as Ex 1, provided that the amounts of water and binder composition used are different and are provided in Table 4. The binder composition used to prepare the coating composition is provided in Table 6.

Comp Ex F and G coating compositions

The coating composition with 17% PVC was prepared according to the same procedure as for preparing the 60% PVC coating composition, based on the formulation given in Table 5. The binder composition used to prepare the coating composition is provided in Table 6.

The obtained coating composition was tested for beading effect and antifouling properties according to the test method described above and the results are provided in Table 6.

As shown in Table 6, both the coating composition of Comp Ex AD and Ex 1 had 60% PVC and included 6% wax. The coating composition of Comp Ex A and D comprising emulsion polymers each prepared with a non-reactive surfactant (DS-4) or a conventional reactive surfactant (SR-10), both coated film having any beading effect. It was not provided (beading effect score: 0). The coating compositions of Comp Ex B and C comprising emulsion polymers made with reactive phosphate surfactants (MAXEMUL 6112 and PP-7025, respectively) provided only coating films with a beading effect score of 2.5. In contrast, the coating composition of Ex 1 with 60% PVC comprising an emulsion polymer made with an AR-1025 reactive surfactant provided a coating film with surprisingly good beading effect (beading effect score: 5). At the same time, the coating film of Ex 1 also showed much better or comparable antifouling properties than other binders with conventional non-reactive or reactive surfactants. In addition, all coating compositions of Ex 2-9 with emulsion polymers made of AR-1025 with wax loading in the range of 2% to 15%, even up to 68%, all had a beading effect score of 4 or higher. A coating film having a good beading effect was provided.

In addition, coating compositions comprising emulsion polymers made with DS-4 surfactant (Comp Ex E) or AR-1025 surfactant (Comp Ex F) without E340 wax have no beading effect even at low PVC content (17% PVC). It has been found to provide a coating film. A coating composition of Comp Ex G made of AR-1025 surfactant but containing an emulsion polymer with 1% wax provided a coating film with an unsatisfactory beading effect. The coating composition of Comp Ex H with 71% PVC produced a coating film with a beading effect score of only 2.

Therefore, it is believed that the synergistic effect between AR-1025 surfactant, wax and pigment surprisingly resulted in an improved beading effect and good antifouling properties.

Claims (9)

(A) based on the dry weight of the emulsion polymer, an emulsion polymer comprising structural units of a polymerizable surfactant having the structure of formula (I):

(I)
Here, R ₁ is a phenyl group or a phenyl substituted alkyl group; m1 is 1, 2, 3 or 4; R ₂ is alkyl or substituted alkyl; m2 is 0 or 1; R ₃ is hydrogen or a C ₁ -C ₂₀ alkyl group; R ₄ is hydrogen or a C ₁ -C ₂₀ alkyl group; A represents an alkylene group or a substituted alkylene group having 2 to 4 carbon atoms, n is an integer ranging from 1 to 100, X is hydrogen, or-(CH ₂ ) _a -SO ₃ M,-( CH ₂ ) _b -COOM, -PO ₃ M ₂ , -P (Z) O ₂ M, or -CO-CH ₂ -CH (SO ₃ M) -COOM (where a and b are each independently 0-4 Is an integer, Z represents a residue obtained by removing X from formula (I), each M is an anionic hydrophilic group selected from hydrogen, alkali metal atom, alkaline earth metal atom, ammonium residue, or alkanolamine residue) An emulsion polymer exhibiting;
(B) a wax emulsion in an amount of 1.1 to 20% by weight solids based on the dry weight of the emulsion polymer; And
(C) An aqueous coating composition comprising a pigment,
The aqueous coating composition has a pigment volume concentration of 56% to 70%, aqueous coating composition. The aqueous coating composition of claim 1, wherein the emulsion polymer comprises from 0.5% to 5% by weight of a structural unit of a polymerizable surfactant, based on the dry weight of the emulsion polymer. The method of claim 1, wherein the polymerizable surfactant has a structure of formula (I), wherein R ₁ is

And m ₁ is 1, 2, or 3, aqueous coating composition. The aqueous coating composition according to claim 1, wherein A represents an ethylene group and n is an integer ranging from 5 to 20. The aqueous coating composition of claim 1, wherein the wax emulsion is a paraffin wax emulsion. The aqueous coating composition of claim 1, wherein the wax emulsion is present in an amount of 2 to 6% by weight solids based on the dry weight of the emulsion polymer. The aqueous coating composition according to claim 1, wherein the emulsion polymer has a glass transition temperature of 0 ° C to 50 ° C. The aqueous coating composition of claim 1, wherein the aqueous coating composition has a pigment volume concentration of 58% to 68%. As a method of improving the beading effect of the substrate,
Forming the aqueous coating composition of any one of claims 1 to 8,
Applying the aqueous coating composition to a substrate, and
Drying the aqueous coating composition, or drying the composition,
The coated substrate has an improved beading effect.